Aldehyde and antioxidant agent and process



Patented June 24, 1930 UNITED; :STATES PATENT OFFICE -HAROLD A. MORTON, OF AKRON, OHIO No Drawing.

hydes, acids.

ALDEHYDE AND ANTIOXIDANT ,AGEN'I. AND PROCESS Application filed August 17, 1928. Serial No. 300,371.

experienced in f various aldeination of the aldehyde with undesirable acids; in the destruct on the containers; an

ive action of the acid d in the discoloration of the product and accumulation of impurities due to the corrosive action of the acid on the metal container.

My invention relat prevention of the oxi es to the retardation or dation of aldehydes by the addition of a material possessing antioxidant properties.

According to my invention,

the aldehyde or aldehyde solution to be preserved has as an \added ingredient a small quantity ofa derivative of hydroglyoxaline.

There are a great number of such hydros y manner.

oxaline derivatives which function in this These derivatives are designated 1n this specification by the accustomed nomenclature now in general use. terial, glyoxahne, stances are derived The basic mafrom which these subusually given the following chemical formula:

The substances described in this specificaare cmz 0 -NH/ tion are hydroglyoxalines or substituted hydroglyoxalines and their derivatives.

In general they may be prepared by heating a 1-2 diamino ethane derivative with the desired aldehyde, although other methods of preparation may be employed.

As examples 0 which have been properties I may ment -5 trip -5 trl -5 trl tolyl rink di di di (11 (11 di (11 d1 phenyl di hydroglyoxaline tetra hydroglyoxaline ortho tolyl tetra hydroglyoxaline para tolyl tetra hydroglyoxallne xylyl tetra alpha 11a ht beta nap thy phenyl ortho tolyl tetra phenyl alpha naphthyl tetra hydroglyoxalme phenyl' 2-methy1 tetra hydroglyoxaline phenyl 2-vlnyl tetra hydroglyoxahne phenyl 2 -propy1 tetra h hydroglyoxallne hyl tetra hydroglyoxaline 1 tetra hydroglyoxaline hydroglyoxaline ydroglyoxaline di phcnyl 4-pseudo butyl tetra hydroglyoxaline d1 phenyl 2-propcnyl tetra hydroglyoxaline (1i phenyl 2-fury1 tetra hydroglyoxaline d phenyl 2-hexyl tetra hydroglyoxaline d1 phenyl 3-beta naphthyl tetra hydroglyoxaline phenyl beta naphthyl 2-fury1 tetra hydroglyoxaline d1 alpha naphthyl 2-propyl tetra hydroglyoxaline -3 triphenyl tetra hydroglyoxaline phenyl 2-methoethyl tetra hydroglyoxaline ortho tolyl 2-propyl tetra hydroglyoxal'ine para tolyl 2-methy1tetra hydroglyoxaline xylyl 2-fury1 tetra hydroglyoxaline lpha naphthyl 2-propenyl tetra hydroglyoxaline d1 lpha naphthyl 2-pheny1 tetra hydroglyoxaline di beta naphthyl 2-methyl tetra hydroglyoxaline phenyl ortho tolyl 2-propy1 tetra hydroglyoxaline 1 d phenyl .4-methy1 tetra hydroglyoxaline d ortho tolyl 4-methyl tetra hydroglyoxaline para tolyl 4-methy1 tetra hydroglyoxaline I yl 4-methy1 t'etra hydroglyoxaline d1 lpha na hthyl 4-methyl tetra hydroglyoxaline di eta nap thyl 4-methy1 tetra hydroglyoxaline d1 henyl 4-ethyl tetra hydroglyoxaline ara tolyl 4-ethyl tetra hydroglyoxaline ha naphthyl 2-methyl tetra hydroglyoxaline henyl 2-propy1 4-methy1 tetra hydroglyoxaline 3 henyl para tolyl 2-thio tetra hydroglyoxaline -3 di henyl 2-thio tetra hydroglyoxaline ortho tolyl xylyl 2-thio tetra hydroglyoxaline di phenyl 2-thio it-methyl tetra hydroglyoxaline di phenyl 2-thio 4-5-dlmethyl tetra hydroglyoxaline (1i phenyl 2-4-dimethyl tetra hydroglyoxaline -3 (1i phcnyl 2-viny1 4-methyl tetra hydroglyoxaline 3 di phenyl 2-propenyl 4-methyl tetra hydroglyoxaline di phenyl 2-furyl 4-methyl tetra hydroglyoxaline di phenyl 2-hexy1 4-methy1 tetra hydroglyoxaline di phenyl 2-meth0ethy1 4-methyl tetra hydroglyoxaline -3 triphenyl 4-methyl tetra hydroglyoxaline ortho tolyl 2-4-dimethy1 tetra hydroglyoxaline para to] 1 2-propyl Jr-methyl tetra hydroglyoxaline xylyl 2- uryl 4-methyl tetra hydroglyoxaline e 1-3 ta naphthyl 2-propenyl 4-methyl tetra hydroglywpge a' phenyl 4-5-dimethyl tetra hydroglyoxaline phenyl 2-methyl 4-ethyl tetra hydroglyoxaline ortho tolyl 2-vinyl 4-ethyl tetra hydroglyoxaline xylyl 2-propyl 4-ethyl tetra hydroglyoxaline alpha naphthyl 2-pheny1 4-ethyl tetra hydroglyoxaphenyl 4-4-dimethyl tetra hydroglyoxaline iortho tolyl 4-4-dimethy1 tetra hydroglyoxaline ipara tolyl 4-4-d imethyl tetra hydroglyoxaline ixylyl 4-4-dimethyl tetra hydroglyoxaline ialpha naphthyl 4-4-g1imethyl tetra hydroglyoxaline ibeta naphthyl 4-4-dimethyl tetra hydroglyoxaline 1 phenyl 2-propyl 4-pseudo butyl tetra hydroglyoxaline iphenyl 2-4-5-trimethy1 tetra hydroglyoxaline r: maintainer; "m

glyoxahne I 3 di beta na hthyl 2-4-5-trimethyl tetra hydroglyoxalme -3 diphenyl -4-4-trimethy1 tetra hydroglyoxaline 1-3 (1i phenyl 2-vinyl 4-4-djmethy1 tetra hydroglyoxalinei-2-3-triphenyl 4-4-dimethy1 tetra hydroglyoxahn'e di alpha naphthyl 2-phenyl 4-methy1 tetra hydroglyoxiphenyl 2-propenyl 4-5-dimethyl tetra hydroglyoxa- 4-5-dimethyl tetra hydroglyoxaline 3 di ortho tolyl 2-propy1 4-4-dimethyl'tetra hydroglyoxa- A line 1-3 di phenyl 4-4-5-trimethyl tetra hydroglyoxaline 1-3 (11 phenyl 2-4-4-5-tetra meth l tetra hyflroglyoxaline 1-2pm phenyl 1-2-propy1 4-4-5-t methyl tetra hydroglyoxame 1-2-3-tripheny1 4-4-5-trimethyl tetra hydroglyoxaline As indicated in the foregoing examples,

H, s, CH3, CH CH ci-ncrncriz, cH. .oH, cmcrncrigorn, 0H, 011.011., CH3CH2CH2CH2CH2, c113 CH.CH CH C H C H CH C H (CH C6-H5CH2, CH3 CH CH CH=C(C2H C H O, .CH CIL CH CH CH CH or in general any aliphatic or aromatic groups, whether saturated or unsaturated. These radicals I consider members of the class which may be designated, and in some of the appended claims are identified by the term, 2 modifying group. v

Independent of the special member which may be used in 2 modifying group, one or more of the hydrogen atoms which are attached to the nitrogen atoms in the 1-3 posi- "ing:

tions may be replaced by any of the follow- CH3, (atom, orncmoit, cusncfl,

CH CH CH CH (CH CH.CH CI-LCI-I CH CH CH (CH CH.CH CH C H C H CH C H (CH C H CH CH CH=CH, CH =CH, CH CH CH CH= C (C 11 C H O, CH CH CH CH CH CH or in general any aliphatic or aromatic group, whether saturated or unsaturated. These radicals I consider members of a class which may be designated and in some of the appended claims are identified by the term, 1-3 replacement group.

One or both of the O atoms may also in the 4-5 positions have attached thereto one or more of the following:

H, CH CH CH CH CH CH '(CH CH, CH CH CH CH (CH (HIGH- CH H C H CH C H (CH l H CH CH CH=CH, CH =CH, CII CH CH CH=C (C H C H O, CH CH CH CH- .CH. ,CH or in general any aliphatic or aromatic group, Whether saturated or unsaturated. These I consider members of a class which may be designated and in some of the appended claims I have identified by the term, 4-5 modifying group.

It is to be understood, however, that strongtemperature.

For example it is not only possible to use the free bases of the above series but it is also possible to use salts and soaps formed from these materials Without materially a-lfecting the anti-oxidant value.

One of the preferred members of the above series is 1-3 diphenyl 2-propyl tetrahydroglyoxaline. One method. of preparing this material is to heat 100 parts of 1-2 di (phenyl amino) ethane dissolved in alcohol with 40 parts of butyraldehyde under reflux for several hours. Upon cooling and crystallizing there is obtained a'cream colored solid, which is dried and is then ready for use.

The tetra hydroglyoxaline derivatives referred to in this specification are prepared in general by the action of aldehydes on the corresponding 1-2 diamino ethane derivatives and are considered to have the glyoxaline constitution as given. However, I do not wish to be bound by any of the theories or constitutions given in this specification but desire to protect the class of materials formed in this manner.

The thio tetra hydroglyoxaline derivatives are prepared in general by the action of carbon disulphide. on the corresponding 1-2 diamino ethane derivatives and are .considered to have the hydroglyoxaline constitution.

.However, I do not wish to be bound by this theory but desire to claim that class of materials formed by the reaction of thio carbonyl chloride and 1-2 diamino ethane derivatives.

The amount of the material which is used may vary considerably, but it has been found that quantities ranging from 0.25% to 1.0% produce good results. Of course a smaller amount of material may be used if this preserving action need not be so great and correspondingly the quantit may be increased considerably above 1% i it seems desirable.

In general the compounds of this invention'are easily prepared and some member of the group is soluble in each of the common aldehydes. The activity of these materials is not destroyed by a relatively high In general these compounds impart no undesirable characteristics to the aldehydes.

The process may be used in any place where it is desirable to prevent the oxidation of aldehy-des, whether this be during storage and handling or during the course of chemical reactions.

The process of this invention may also be practiced with any material which contains aldehyde groups and which has a tendency to become oxidized.

To illustrate the manner in which the foregoing materials may be used and the eflect which they have on the oxidation of aldehydes the following examples are given:

, Example! A sample of butylaldehyde contained in a small flask equipped with a reflux condenser was treated with a comparatively rapid stream of dry oxygen at ordinary temperature. The same conditions were used in a series of other flasks containing butylaldehyde in the presence of various substituted hydroglyoxaline and the rate of oxidation measured by analyzing the butylaldehyde at regular intervals for the amount of butyric acid formed.

The difference in oxidation is also ,very readily noted by the relative change in temperature. The butylaldehyde containing no anti-oxidant, developed considerable heat as oxidation progressed, whereas, the butylaldehyde samples in the presence of these antioxidants showed no appreciable increase in temperature.

The amount of butyric acid was determined at the end of a six hour period of treatment with oxygen. In all cases 0.5% of anti-oxidant was employed.

In the present example the control, which consisted of butylaldehyde in the absence of an anti-oxidant, showed an acidity of 36.5% butyric acid at the end of the six hour oxidation period.

,The following table gives the acidity at the end of this six hour period, for members of this class of compounds.

Anti-oxidant: 2-4-5 trifuryl di hydroglyoxaline Acidity 2.1% Anti-oxidant: 1-3 diphenyl 2-methy1 tetra hydroglyoxaline Acidity 1.1% Anti-oxidant: 1-3 diphenyl 2-propy1 tetra hydroglyoxallne Acidity O.8% Anti-oxidant: 1-3 diphfinyl 2-propenyl tetra hydroglyoxane Acidity 1.2% Anti-oxidant: 1-3 diphenyl 2-propy1 4-methy1 tetra hydroglyoxaline Acidity 0.7% Anti-oxidant: 1-3 diphenyl 2-4-5 trimethyl tetra hydroglyoxaline Acidity 1.1% I Anti-oxidant: 1-3 di alpha naphthyl 2-propyl 4-5 dimethyl 87 tetra hydroglyoxaline Z a Acidity I Example I I To illustrate the use of these materials for the prevention of oxidation of benzaldehyde to benzoic acid the following example is given:

The method of procedure was the same as that given in Example 1, except that a period of 24: hours treatment with oxygen was employed. At the end of this period the benzaldehyde containing '10 anti-oxidant material contained 10.1% of benzoic acid.

The effect of several of these anti-oxidant materials in a 24: hours oxidation period is shown in the following table:

Anti-oxidant: 1-3 diphenyl tetra hydroglyoxaline Acidity a 1-3 diphenyl 2-propyl tetra hydroglyoxaline Anti-oxidant 1'-3 diphenyl 2-propyl 4-methyl tetra hydro- Acidity Anti-oxidant glyoxalme Acidity 2.45

The above examples are illustrative of the What I claim is:

1. The method of retarding the oxidation of aldehydes which comprises adding to the aidehyde a derivative of hydrogenated glyoxa me.

2. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a derivative of di hydroglyoxaline.

3. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a derivative of tetra hydroglyoxaline.

4. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a di-aryl tetra hydroglyoxaline.

The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a tetra hydroglyoxaline derivative the 1-3 positions and an aliphatic radical in I the 2 position.

8. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a derivative of tetra hydroglyoxaline wherein the carbon atom in the 2 position has attached thereto a radical which is a member of the 2 modifying group, substantially as described.

9. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a tetra hydroglyoxaline derivative wherein the carbon atom in the 2 position has attached thereto an aliphatic radical.

10. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a tetra hydroglyoxaline derivative wherein the carbon atom in the 2 position has attached thereto a propyl radical.

11. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a tetra hydroglyoxaline derivative wherein one of the hydrogen atoms attached to the nitrogen atoms in the 1 or 3 positions is replaced by a radical which is a member of the 1-3 replacement group.

12. The method of retarding the-oxidation of aldehydes which comprises adding to the aldehyde a tetra hydroglyoxaline derivative wherein one of the hydrogen atoms attached to the nitrogen atoms in the 1 or 3 positions is replaced by an aliphatic radical.

' 13. The method of retarding the' oxidation of aldehydes which comprises adding to the aldehyde a derivative of tetra hyclroglyoxaline wherein one of the hydrogen atoms line wherein one of the hydrogen atoms atto the nitrogen atoms in the 1-3 group.

tached to the nitrogen atoms in the l or 3 positions is replaced by a phenyl radical.

15. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a derivativeof tetra hydroglyoxaline wherein each hydrogen atom attached to the nitrogen atoms in the 1-3 positions is replaced by a radical which is a member of the 1-3 replacement group.

' 16. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde the product prepared by condensing a derivative of 1-2 diamino ethane with an aldehyde. I

17 l The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a tetra hydroglyoxaline derivative wherein both hydrogen atoms attached to the nitrogen atoms in the 1-3 positions are replaced by an organic radical.

18. The method of retarding the oxidation of aldehydes which. comprises adding to the aldehyde a derivative of tetra hydroglyoxa line wherein both hydrogen atoms attached positions are replaced by an aromatic radical.

19. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a derivative of tetra hydroglyoxaline wherein both hydrogen atoms attached to the nitrogen atoms in the 1-3 positions are replaced'by a phenyl radical.

20. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a derivative of tetra hydroglyoxaline wherein each of the carbon atoms in the 4-5-positions has a radical attached thereto which is a member of the 4-5 modifying 21. The method of retarding the oxidation of aldehydes which comprises adding to the aldehyde a derivative of tetra hydroglyoxaline wherein each of the carbon atoms in the 4-5 positions has two radicals attached thereto both of which are members of the 4-5 modifying group.

22.. The method of retarding the oxidation I of aldehydes which comprises adding to the aldehyde a derivative of tetra hydroglyoxaline wherein each of the carbon atoms in the 4-5 positions has a hydrogen atom attached thereto.

23. The method of retarding the oxidation aldehyde 1-3 diphenyl 2-propyltetra hydroglyoxaline.

In testimony whereof, I afiix my signature.

HAROLD A. MORTON.

of aldehydes which comprises adding to the aldehyde a derivative of tetra hydroglyoxaline wherein each of the-carbon atoms in the 

